WO2008050852A1 - Film photocatalyseur mince à base d'oxyde de tungstène - Google Patents

Film photocatalyseur mince à base d'oxyde de tungstène Download PDF

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Publication number
WO2008050852A1
WO2008050852A1 PCT/JP2007/070880 JP2007070880W WO2008050852A1 WO 2008050852 A1 WO2008050852 A1 WO 2008050852A1 JP 2007070880 W JP2007070880 W JP 2007070880W WO 2008050852 A1 WO2008050852 A1 WO 2008050852A1
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WO
WIPO (PCT)
Prior art keywords
thin film
oxide thin
tungsten oxide
sputtering
gas flow
Prior art date
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PCT/JP2007/070880
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English (en)
Japanese (ja)
Inventor
Yoshinori Iwabuchi
Masato Yoshikawa
Yuzo Shigesato
Mizuki Fukuyama
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Bridgestone Corporation
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Publication of WO2008050852A1 publication Critical patent/WO2008050852A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/347—Ionic or cathodic spraying; Electric discharge
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/083—Oxides of refractory metals or yttrium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/228—Gas flow assisted PVD deposition

Definitions

  • the present invention relates to a tungsten oxide (WO) thin film, and more particularly to gas flow sputtering.
  • WO tungsten oxide
  • the present invention relates to a tungsten oxide thin film having a visible light responsive photocatalytic function formed by high-speed film formation.
  • Tungsten oxide is an excellent photocatalytic material, and its functions such as decomposing organic matter and super-hydrophilicity, deodorization, water purification, antifouling, self-cleaning (self-cleaning), antibacterial, anti-wineless, anti-mold, Application to various fields such as sterilization has been attempted.
  • crystalline tungsten oxide is expected to be used not only outdoors but also indoors because it has visible light responsiveness that shows catalytic activity under visible light.
  • tungsten oxide When tungsten oxide is applied to a photocatalytic material, it is rarely used alone, and it is usually used after being fixed in the form of a thin film on the surface of some substrate. At this time, sputtering has the advantage that a tungsten oxide thin film can be formed on any substrate surface with good adhesion, and is an excellent method for forming a tungsten oxide thin film.
  • the conventional sputtering has a slow deposition rate! /
  • it shows visible light response only when the substrate is deposited while being heated to about 600 ° C or higher, and the low temperature is low.
  • post-baking is carried out after the film is formed, the fact that the visible light response is not exhibited is also a problem in that the manufacturing method is limited.
  • the film formation speed is slow; only when the film is formed while heating the substrate to about 600 ° C or higher. Visible light responsiveness, and after firing after film formation at low temperature, it does not show visible light responsiveness; in addition, in normal sputtering, the vacuum chamber is evacuated to a high vacuum state. In order to do so, it requires a large force, a simple exhaust device and a high-performance control device, so there is a disadvantage that expensive equipment is required.
  • Gas flow sputtering is a method in which sputtering is performed under a relatively high pressure, and sputtered particles are transported and deposited to a film formation target substrate by a forced flow of a gas such as Ar. Since this gas flow sputtering does not require high vacuum evacuation, it is possible to form a film by mechanical pump exhaust without using a large exhaust force and a conventional exhaust device such as conventional sputtering. Can be implemented with inexpensive equipment. Moreover, gas flow sputtering can form films 10 to 1000 times faster than normal sputtering.
  • the target utilization efficiency is approximately 20-30% in normal sputtering, which requires a magnet on the back of the target, whereas in the gas flow sputtering, the target is utilized.
  • the efficiency is very high at over 90%. Therefore, according to gas flow sputtering, it is possible to significantly reduce the deposition cost by reducing the equipment cost, shortening the deposition time, and improving the efficiency of using the target.
  • Patent Document 1 JP 2006-130378
  • Patent Document 2 JP 2006-134602
  • An object of the present invention is to provide a photocatalytic tungsten oxide thin film formed at low cost by high-speed film formation.
  • the present inventors have been able to form a tungsten oxide thin film at a low cost by high-speed film formation by employing gas flow sputtering. It was found that a tungsten oxide thin film having excellent visible light responsive photocatalytic activity can be obtained both in the case of forming a film while heating the film and in the case of post-baking the formed tungsten oxide thin film. Was completed.
  • the gist of the present invention is as follows.
  • the tungsten oxide thin film according to the first aspect is characterized by being formed by gas flow sputtering.
  • the tungsten oxide thin film according to the second aspect is characterized in that, in the first aspect, metal tungsten is used as a target and is formed by reactive sputtering in which oxygen gas is introduced.
  • the tungsten oxide thin film according to the third aspect is characterized in that, in the first or second aspect, the tungsten oxide thin film is formed on a heated base material and exhibits photocatalytic activity with an azposition.
  • the tungsten oxide thin film of the fourth aspect is characterized in that, in the third aspect, a glass plate, a metal plate, a metal foil or a ceramic plate is used as a substrate.
  • the tungsten oxide thin film according to the fifth aspect is characterized in that any force of the first to fourth aspects, and in one aspect, a film forming pressure force in gas flow sputtering is about ⁇ 200Pa.
  • the tungsten oxide thin film according to the sixth aspect is formed by gas flow sputtering in which the argon gas and the oxygen gas are separately introduced in any one of the first to fifth aspects. It is what.
  • the tungsten oxide thin film of the seventh aspect is formed by a gas flow sputtering apparatus having a force sword structure in which the rectangular target is arranged to face each other in any one of the first to sixth forces. It is characterized by this.
  • the tungsten oxide thin film of the eighth aspect is any one of the first to seventh forces, in one aspect, the gas The film is formed by flow sputtering at a film formation speed of 100 nm / min or more.
  • the tungsten oxide thin film according to the ninth aspect is characterized in that in any one of the first to eighth aspects, in one aspect, the film is fired after film formation by gas flow sputtering.
  • the tungsten oxide thin film of the tenth aspect is characterized in that, in the ninth aspect, the firing conditions are 400 to 900 ° C.
  • Fig. La is a schematic diagram showing a schematic configuration of a gas flow sputtering apparatus suitable for carrying out the present invention
  • Fig. Lb is a perspective view showing a target and back plate configuration of Fig. La. It is.
  • FIG. 2 is a diagram showing the measurement results of the aldehyde decomposition activity of the tungsten oxide thin film formed in Comparative Example 1.
  • FIG. 3 is a diagram showing the measurement results of the aldehyde decomposition activity of the tungsten oxide thin film formed in Comparative Example 2.
  • FIG. 4 is a graph showing the measurement results of the aldehyde decomposition activity of the tungsten oxide thin film formed in Example 1.
  • FIG. 5 is a graph showing the measurement results of the aldehyde decomposition activity of the tungsten oxide thin film formed in Example 2.
  • FIG. 6 is a diagram in which all the measurement results of the aldehyde decomposition activity of the tungsten oxide thin films formed in Comparative Examples 1 and 2 and Examples 1 and 2 are placed.
  • Gas flow sputtering is a method in which sputtering is performed under a relatively high pressure, and sputtered particles are transported to a deposition target substrate by a forced flow of gas and deposited. Since this gas flow sputtering does not require high vacuum evacuation, it is possible to form a film by mechanical pump exhaust without using a large exhaust force and a conventional exhaust device like conventional sputtering. Therefore, it can be implemented with inexpensive equipment. Moreover, gas flow sputtering can form a film 10 to 1000 times faster than normal sputtering, and has a high utilization efficiency of the target. Therefore, according to the present invention, gas flow sputtering is employed.
  • DC magnetron sputtering gas flow sputtering does not require a magnet on the back of the target. Therefore, the target utilization efficiency is 90% or more, which is very high, which is advantageous for cost reduction.
  • the photocatalytic activity is high! / A film can be formed.
  • the adhesion of the formed tungsten oxide thin film to the substrate is good, a high-quality tungsten oxide thin film can be manufactured.
  • a tungsten oxide thin film can be formed at a high speed without causing a reduction in film formation speed due to an oxide mode as in normal sputtering.
  • the film formation speed varies depending on conditions such as the density of the tungsten oxide thin film being not the same and the film formation pressure. Force that cannot be simply compared When the same power density is applied, a film deposition rate of 20 times or more can be obtained. For example, with a power applied of 4 W / cm 2 , a deposition rate of about 9 nm / min with DC magnetron sputtering and about 200 nm / min with gas flow sputtering is possible.
  • the force of the catalyst activity varies depending on the amount of oxygen introduced and other conditions.
  • the mode change such as a rapid decrease in film formation rate due to the amount of oxygen introduced.
  • the conditions having good photocatalytic activity can be easily found without conversion. Photocatalytic activity tends to be higher as the amount of oxygen introduced increases S, and an excessive increase in the amount of oxygen introduced induces arcing on the target surface, so the oxygen flow rate should be changed appropriately within the range where these problems do not occur. be able to.
  • the gas flow sputtering method is characterized by the ability to form a high-speed film of tandastenite having visible light responsive photocatalytic activity. Furthermore, the tungsten oxide thin film produced by the gas flow sputtering method is heated by substrate heating. In addition to aztepo crystallization, an invention was obtained in which good visible light responsive photocatalytic activity was exhibited even in a crystallization process by post-calcination. For this reason! /, Now it becomes clear! /, N! /, However, the tungsten oxide thin film deposited by gas flow sputtering has a nano-structure that becomes the nucleus of the crystal in the subsequent firing process. There is a possibility that crystals are formed!
  • Fig. La is a schematic diagram showing a schematic configuration of a gas flow sputtering apparatus suitable for carrying out the present invention
  • Fig. Lb is a perspective view showing a target and back plate configuration of Fig. La.
  • a rare gas such as argon is introduced into the chamber 20 from the sputter gas inlet 11 and the anode 13 connected to the power source 12 such as a DC power source and the target 15 serving as a force sword.
  • the target 15 is sputtered by the plasma generated by the discharge in the step, and the sputtered particles that have been blown off are transported to the substrate 16 and deposited by a forced flow of a rare gas such as argon.
  • the substrate 16 is supported by a holder 17, and a reactive gas inlet 18 is disposed in the vicinity of the substrate 16 so that a reactive sputtering ring can be performed.
  • 14 is a water-cooled backing plate.
  • the tungsten oxide thin film is formed by gas flow sputtering by reactive sputtering using metal W as a target and introducing oxygen gas.
  • the shape of the target to be used is not particularly limited. A force that can use a target of an arbitrary shape such as a cylindrical target or a rectangular plate target. Since the processing cost is low, a rectangular plate target is used. It is preferable that these are used as shown in FIG.
  • gas flow sputtering is preferably performed by separately introducing oxygen gas and argon gas as shown in FIG. 1 in terms of high-speed film formation and stable discharge. While forming a film continuously, it is possible to form a film by feeding the sheet-shaped substrate from one roll and winding it around the other roll, and easily increasing the film formation efficiency by increasing the target length. be able to.
  • a heat-resistant substrate is used as the substrate, and for example, a glass plate, a metal plate, a metal foil, a ceramic plate, or the like can be used.
  • the metal of the metal plate and the metal foil include Al, Cu, Au, Fe, Ni and the like, or alloys containing them (for example, SUS).
  • ceramics include zirconia, alumina, yttria, silicon carbide, and silicon nitride.
  • the thin film to be formed becomes a crystalline thin film.
  • the heating temperature is preferably 400 to 900 ° C, particularly 500 to 800 ° C. If it is less than 400 ° C, it will not be sufficiently crystallized. When the temperature is higher than 900 ° C, there are problems such as a limited number of substrates that can be used and a costly heating mechanism.
  • the thin film formed on the non-heated base material without heating the base material at the time of film formation is in a state of azposition (the post-treatment such as post-baking is not performed on the thin film, In the state), it is an amorphous thin film.
  • a thin film formed on this non-heated substrate is fired to form a crystalline thin film.
  • the firing temperature is preferably 400 to 900 ° C, particularly 500 to 800 ° C. If it is less than 400 ° C, it will not be sufficiently crystallized. When the temperature is higher than 900 ° C, there are problems such as a limited number of substrates that can be used and a costly heating mechanism.
  • an underlayer such as an oxide, nitride, or oxynitride of silicon (Si) may be formed on the substrate used for film formation, if necessary.
  • the film formation pressure during gas flow sputtering is too high, the film formation rate will decrease, and arcing will occur easily and become unstable. If it is too low, the discharge voltage will increase and it will be difficult to maintain the discharge. It is preferably 5 to 200 Pa, particularly 10 to 120 Pa.
  • these conditions are set according to high! /, Film formation rate and discharge stability, and photocatalytic activity of the formed tungsten oxide thin film.
  • the film formation rate is the value of the thickness of the film grown per minute.
  • the tungsten oxide thin film obtained as described above was baked after non-heated film formation on the substrate, and was visible for 120 minutes in a test for evaluating the decomposition activity of acetaldehyde listed in the Examples section below. It exhibits catalytic activity that reduces the concentration by light irradiation to 10 ppm or more, preferably 15 ppm or more.
  • the concentration decreased by 15 ppm or more, preferably 20 ppm or more, by 120 minutes of visible light irradiation. Such catalytic activity is exhibited.
  • tungsten oxide having very few oxygen defects and close to the stoichiometric ratio can be formed.
  • Such a photocatalytic tungsten oxide thin film of the present invention has a deodorizing, water purification, antifouling, self-cleaning (self-cleaning), antibacterial, etc. function based on its excellent photocatalytic activity, such as organic matter decomposition and superhydrophilicity. Applicable to various fields such as anti-virus, anti-mold, sterilization
  • Example [0048] The present invention will be described more specifically with reference to the following examples and comparative examples. However, the present invention is not limited to the following examples as long as it does not exceed the gist thereof.
  • the photocatalytic activity of the formed tungsten oxide thin film was evaluated by examining the decomposition activity of acetoaldehyde. This is due to the following reason. In other words, even a sample with a low photocatalytic activity that does not decompose the acetoaldehyde, which is widely evaluated for hydrophilicity as a function of the photocatalyst, may exhibit superhydrophilicity with a contact angle of 5 degrees or less when irradiated with visible light. Therefore, photocatalytic activity was evaluated by examining the decomposition activity of acetaldehyde, which requires higher photocatalytic activity, by the following method.
  • a tungsten oxide thin film with a vertical projection area of 25 cm 2 is placed on a 5 cm square alkali-free glass substrate in a sealed 400 cc quartz glass container so that the concentration is about 60 ppm in the quartz glass container.
  • a xenon lamp with a central wavelength of 450 nm HYASHI “: LA-250Xe xenon lamp”
  • HYASHI LA-250Xe xenon lamp
  • Substrate heating temperature 600 ° C
  • Fig. 2 shows the evaluation results of the decomposition activity of acetoaldehyde in the formed tungsten oxide thin film.
  • the formed tungsten oxide thin film showed the decomposition activity of acetoaldehyde, but the film formation rate was 9 nm / min, which was extremely low.
  • a tungsten oxide thin film was formed in the same manner as in Comparative Example 1 except that the substrate was not heated, and then post-baked at 600 ° C. for 1 hour.
  • Fig. 3 shows the evaluation results of the decomposition activity of acetoaldehyde in the formed tungsten oxide thin film. From Fig. 3, it was confirmed that the formed tungsten oxide thin film did not show the decomposition activity of cetaldehyde.
  • Substrate heating temperature 600 ° C
  • Fig. 4 shows the evaluation results of the decomposition activity of acetoaldehyde of the formed tungsten oxide thin film. From FIG. 4, it was confirmed that the formed tungsten oxide thin film showed an ability to decompose acetoaldehyde at 220 nm / min.
  • a tungsten oxide thin film was formed in the same manner as in Example 1 except that the substrate was not heated. Thereafter, the tungsten oxide thin film was baked at 600 ° C. for 1 hour in the atmosphere.
  • Fig. 5 shows the evaluation results of the decomposition activity of acetoaldehyde of the formed tungsten oxide thin film. From Fig. 5, it was confirmed that the formed tungsten oxide thin film showed the decomposition activity of cetaldehyde.
  • FIG. 6 shows a summary of the results of Comparative Examples 1 and 2 and Examples 1 and 2 (FIGS. 2 to 4). From these results, it is possible to form a tungsten oxide thin film at a high speed with respect to the formation of a photocatalytic tungsten oxide thin film by gas flow sputtering method. It has been clarified that excellent visible light responsive photocatalytic activity (decomposition activity of cetaldehyde) is obtained even by the method of firing!
  • the gas flow sputtering method can be configured with inexpensive equipment, the film formation speed is fast, and the target utilization efficiency is high, so it is possible to produce a photocatalytic thin film at low cost, and WO is not in TiO Since it has visible light responsiveness, it is also promising for indoor use.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
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  • Materials Engineering (AREA)
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  • Plasma & Fusion (AREA)
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  • Optics & Photonics (AREA)
  • Catalysts (AREA)
  • Physical Vapour Deposition (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

La présente invention concerne un film photocatalyseur mince à base d'oxyde de tungstène réalisé par la formation de film à grande vitesse à un faible coût, un film mince à base d'oxyde de tungstène réalisé sur un substrat réchauffé par la pulvérisation cathodique en flux gazeux, et un film mince à base d'oxyde de tungstène réalisé par la formation d'un film par la pulvérisation cathodique en flux gazeux suivie de la cuisson du film. Dans le cas où le film est formé lors du réchauffement du substrat et le cas où le film mince à base d'oxyde de tungstène est soumis à une cuisson ultérieure, il est possible de d'obtenir une meilleure activité photocatalytique de réaction à la lumière visible que par la pulvérisation cathodique à magnétrons en courant continu. La pulvérisation cathodique en flux gazeux est avantageux en ce que la pression est supérieure par environ le double à la pulvérisation cathodique classique, un flux forcé d'un gaz argon s'écoule à la surface d'une cible, la diffusion d'un gaz oxygène sur la surface de la cible est interdite, la pulvérisation cathodique est effectuée tout en maintenant la surface de la cible dans un état métallique frais sans oxydation de la surface de la cible, des particules de pulvérisation sont transportées sur le substrat par un flux forcé d'argon, et les particules de pulvérisation peuvent être oxydées par le gaz oxygène sur le substrat. La configuration selon l'invention permet de réaliser une formation de film à grande vitesse d'un film mince à base d'oxyde de tungstène sans réduction de la vitesse de formation de film due à la formation d'oxyde même en introduisant une quantité suffisante d'oxygène contrairement à la pulvérisation cathodique classique.
PCT/JP2007/070880 2006-10-27 2007-10-26 Film photocatalyseur mince à base d'oxyde de tungstène WO2008050852A1 (fr)

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DE102009057697A1 (de) * 2009-12-03 2011-06-09 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Chemischer Mediensensor, Verfahren zu dessen Herstellung sowie Verwendungszwecke
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